Brown substituted benzidine wool dyestuffs



WILHELM NEELMEIEB, F LEVERKUSEN, NEAR COLOGNE ON-THE-RHINE, GERMANY,

ASSIGNOR T0 GRASSELLI DYESTUFF CORPORATION, OF NEW YORK, N, Y., A COR- FUNCTION 0]? DELAWARE.

BROWN SUBSTITUTED BENZIDINJE WOOL DYESTE'S.

No Drawing. Application filed September 16, 1926, Serial No. 135,994, and in Germany September 25, 1925.

My invention relates to novel disazo dye-- studs and the process of producing same which consists in tetrazotizing certain substituted di-p-amino-diphenyl compoundsand coupling the tetrazo compound obtained with one molecular proportion each of a diamino-disulfonic acid of the benzene serice and of a 2-amino-8-naphtl1ol-6-sulfonic acid compound.

The substituted di-p-amino-diphenyl compounds useful in my novel process are the benzidine derivatives substituted in 2 and 2' position by halogen or an alkyl group the general formula of which is 5 HaN NH:

1: standing for halogen or an alkyl group. Amongst the diamino-disulfonic acids of the benzene series used as -one-of the coupling compounds I might mention as particularly useful the 1-3-phenylenediamine-4-6-disul- SQaH in which R is one of the substituents included in the group comprising the halogen atoms and the alkyl groups, X stands for hydrogen, an alkyl or an aryl" group and Y stands for a diamino-disulfonic acid of the benzene series. These novel dyestufi's are in the form of their alkali metal salts dark brown powders, soluble in water with brown and in concentrated sulfuric acid with reddish-blue colors. They dye animal fibers from an acid bath reddish-brown shades parof excellent fastness to water are produced. W

The shades obtained from my dyestuffs containing 2-alkylor Q-aryl-aminO-S-naphtholfi-sulfonic acids are usually more on the yellowish side than those from the dyestuffs made with the straight Q-amino-S-naphthol- 6-sulfonic acid.

The following examples will further illustrate my invention, the parts being by weight.

Example 1.'253 parts Q-Q dichJorO-T-QV- diamino-diphenyl (dichlorbenzidine) are tetrazotized in the usual manner with 138 parts sodium nitrite and the requisite amount of hydrochloric acid. The so obtained solution of the tetrazo compound is run into an ice cold solution of 268 parts 1-3-phenylene-diamine 4-6-disulfonic acid, keeping the reaction mass all the time acetic acid; the coupling is finished after about hour and the intermediate compound separates. The

reaction mass is now made soda alkaline with continued cooling and a solution of 2-amino- S-naphthol-G-sulfonic acid containing an excess of sodium carbonate added all at once.

The product is stirred until the second coupling is finished. I TheJdyeStuE is then salted out, filtered off and dried. The so obtained product is a dark brown powder, soluble in water with a reddish-brown and in concentrated sulfuric acid with a bluish-red color. W

By direct printing on woolen or silk goods it produces reddish-brown shades of excellent tastness to water. It has in the free state most probably the formula:

N'Hz @0918 NE? sogn memes and the reaction mass left standing for several hours at 0 C. until the coupling is completed. The dyestufi is then salted out, filtered off and dried. It is a dark brown powder, soluble in water with a reddishbrown and in concentrated sulfuric acid with a bluish-red color. It dyes wool and silk reddish-brown shades and produces by direct printing on woolen and silk material full reddish-brown shades of excellent fastness to water. It has in the free state most probably the formula:

on H N N N-N-O Ha CH3 NH: 03H som Example 3.253 parts 2-2dich1oro-4-4- diamino-diphenyl are tetrazotized in the usual manner and the tetrazo compound first coupled as described in Example 1 with 268 parts l-3-phcnylene diamine-4-6 disulfonic acid; the intermediate compound is then coupled in soda-alkaline solution with 252 parts 2-methylamino-8-naphthol 6 sulfonic acid. The dyestulf isolated in the usual manner is I claim:

1. In processes of producing brown disazo dyestufis the steps comprising tetrazotizing substituted diamino-diphenyl compounds of the formula:

in which R is a halogen atom or an alkyl group .and coupling successively and in any chosen order the tetrazo compound obtained with a mono molecular proportion of a diamino-disulfonic acid of the benzene series and in alkaline solution with a mono molecular proportion of a 2-.amino-8-naphthol-G-sulfonic acid compound of the formula:

sons in which X stands for hydrogen, an alkyl or an aryl group.

2. In processes of producing brown disazo dyestuffs the steps comprising tetrazotizing a dark brown powder, soluble in water with a reddish-brown and i "concentrated sulfuric acid with a bluish-red color. Dyed on wool in an acid bath or printed on woolen or silk material it produces fast brown shades, which compared with those obtained from the dyestuffs of Examples 1 and 2 are more yellowish. It has in the free state most probably the formula:

substituted diamino-diphenyl compounds of the formula:

in which R stands for chlorine or an alkyl group and coupling successively and in any chosen order the tetrazo compound obtained with a mono molecular proportion of a m-phenylenediamine-disulfonic acid and in alkaline solution with a 2-amino-8-naphthol- 6-sulfonic acid compound of the formula:

i, BOuE in which hydrogen, an alkyl or an aryl group.

3. In processes of producing a brown disazo dyestufi the steps comprislng tetrazotizing 2-2 -d1chloro- 1-4 -d1am1no-d1phenyl and coupling the tetrazo compound obtained with a mono molecular proportion of 1-3-phenylenediamine-4-6-disulfonic acid and in alkaline solution with a mono molecular proportion of 2-amino-S-naphthol-G-sulfonic acid.

stufi's having in the free state most probably 4:. As new products brown disazo dyethe formula:

soluble in water with reddish-brown and in concentrated sulfuric acid with bluish-red colors and dye animal fibers fast brown shades.

5. As new products brown disazo/dyestuffs having in the free state most probably the formula:

H\ on B R SOsH in which R is a chlorine atom or an alkyl group, X stands for hydrogen, an alkyl or an aryl group and Y stands for a metaphenylene-diamine-disulfonic acid, which are in the form of their alkali metal salts dark brown powders, soluble in water with C1 01 NH O H which in the form of its alkali metal salts is a dark brown powder, soluble in Water with a reddish-brown and in concentrated sulfuric acid with a bluish-red color,

reddish-brown and in concentrated sulfuric acid with bluish-red colors and dye Wool and silk brown fast shades.

6. As a new product the disazo dyestufi having in the free state most probably the formula:

dyeing wool and silk fast brown shades. In testimony whereof, I afiix my signature.

WILHELM N EELMEIER. 

